0585909 - ÚACH 2025 RIV GB eng J - Journal Article
Škoch, Karel - Antala, J. - Císařová, I. - Štěpnička, P.
Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues.
Dalton Transactions. Roč. 53, č. 20 (2024), s. 8722-8731. ISSN 1477-9226. E-ISSN 1477-9234
Institutional support: RVO:61388980
Keywords : coordinated phosphorus-compounds * heterocyclic carbene complexes * cross-coupling reactions * c-h bond * oxidative-addition * structural-characterization * suzuki-miyaura * chiral ferrocenyl * (nhc)pd(allyl)cl nhc * allylic substitution
OECD category: Inorganic and nuclear chemistry
Impact factor: 3.5, year: 2023
Method of publishing: Open access

Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl pi-donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/pi-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz. [PdCl(R(2)PfcCHCHCH(2)-eta(3):kappa P)] (1 (R), R = Ph and cyclohexyl (Cy), fc = ferrocene-1,1 '-diyl). These compounds were synthesized from the respective phosphinoferrocene carboxaldehydes R(2)PfcCHO via reaction with vinylmagnesium bromide to generate 1-(phosphinoferrocenyl)allyl alcohols, which were subsequently acetylated. The resulting allyl acetates reacted smoothly with [Pd-2(dba)(3)]/[Et3NH]Cl (dba = dibenzylideneacetone) to produce the target compounds. Complexes 1 (R) and their nontethered analogues [PdCl(eta(3)-C3H5)(FcPR(2)-kappa P)] (5 (R), Fc = ferrocenyl) were evaluated as pre-catalysts for the Pd-catalysed allylic amination of cinnamyl acetate with aliphatic amines and Suzuki-Miyaura-type cross-coupling of 4-tolylboronic acid with benzoyl chloride. In these reactions, better results were achieved with compounds 5 (R) (particularly with 5(Ph)), presumably because they form more stable LPd(0)-type catalysts.
Permanent Link: https://hdl.handle.net/11104/0353760


Research data: CCDC, CCDC